JPH0263055A - Polymer composition sensitive for radiation - Google Patents
Polymer composition sensitive for radiationInfo
- Publication number
- JPH0263055A JPH0263055A JP21577288A JP21577288A JPH0263055A JP H0263055 A JPH0263055 A JP H0263055A JP 21577288 A JP21577288 A JP 21577288A JP 21577288 A JP21577288 A JP 21577288A JP H0263055 A JPH0263055 A JP H0263055A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- group
- radiation
- propargyl
- sensitizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 103
- 230000005855 radiation Effects 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims description 18
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims abstract description 28
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 18
- 230000002140 halogenating effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229920013730 reactive polymer Polymers 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 229920002125 Sokalan® Polymers 0.000 abstract description 6
- 239000004584 polyacrylic acid Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000005427 anthranyl group Chemical group 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- -1 poly(hydroxystyrene) Polymers 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- FCETXLHFBYOVCV-UHFFFAOYSA-N 2-(bromomethyl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CBr)=CC=C3C(=O)C2=C1 FCETXLHFBYOVCV-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000008365 aromatic ketones Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- XAMMUQHFUJWZQX-UHFFFAOYSA-N 2-(bromomethyl)anthracene Chemical compound C1=CC=CC2=CC3=CC(CBr)=CC=C3C=C21 XAMMUQHFUJWZQX-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- QEMMTKPYWRKLME-UHFFFAOYSA-N 3-fluoroprop-1-yne Chemical compound FCC#C QEMMTKPYWRKLME-UHFFFAOYSA-N 0.000 description 1
- WGCICQJXVYFFCA-UHFFFAOYSA-N 3-iodoprop-1-yne Chemical compound ICC#C WGCICQJXVYFFCA-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は放射線感応性重合体組成物に関し、さらに詳細
には、可視光線、紫外線、遠紫外線、電子線、X線、イ
オン線、分子線、γ線、シンクロトロン放射線、プロト
ンビームなどの放射線に感応するネガ型レジストとして
好適な放射線感応性重合体組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a radiation-sensitive polymer composition, and more particularly, it relates to a radiation-sensitive polymer composition that is sensitive to visible light, ultraviolet rays, deep ultraviolet rays, electron beams, X-rays, ion beams, and molecular beams. The present invention relates to a radiation-sensitive polymer composition suitable as a negative resist sensitive to radiation such as γ-rays, synchrotron radiation, and proton beams.
[従来の技術]
従来、半導体集積回路などの製造においては、基板の上
にレジストを塗布し、部分的に放射線を照射し、さらに
現像することにより微細レジストパターン形成し、次い
でレジストパターン部以外の基板部分をエツチングする
ことが行なわれる。[Prior Art] Conventionally, in the manufacture of semiconductor integrated circuits, etc., a fine resist pattern is formed by coating a resist on a substrate, partially irradiating it with radiation, and developing it. Etching of the substrate portion is performed.
このような放射線による一連のバターニング工程におい
て使用するレジストは、放射線に対して高い感応性を有
し、微細なレジストパターンを高精度に形成することが
でき、かつエツチングに対して高い耐性を有することが
必要である。The resist used in this series of radiation patterning processes has high sensitivity to radiation, can form fine resist patterns with high precision, and has high resistance to etching. It is necessary.
[発明が解決しようとする問題点]
近年、プロパルギル基を有する重合体と光ラジカル開始
剤を配合してなる放射線感応性重合体組成物が照射によ
って架橋することが報告されている(高分子論文集第3
7巻、249〜254頁、1980年、特開昭62−2
53152号公報)。[Problems to be solved by the invention] In recent years, it has been reported that a radiation-sensitive polymer composition comprising a polymer having a propargyl group and a photoradical initiator is crosslinked by irradiation (Kobunshi Papers Collection 3
Vol. 7, pp. 249-254, 1980, JP-A-62-2
53152).
該放射線感応性重合体組成物は、酸素の存在下、例えば
空気中では著しく放射線に対して感応性が低下するとい
う欠点がある。The radiation-sensitive polymer compositions have the disadvantage that they become significantly less sensitive to radiation in the presence of oxygen, for example in air.
[問題点を解決するための手段]
本発明は、
(1)側鎖にプロパルギル基および/または置換プロパ
ルギル基ならびに増感基を有する重合体(以下、「重合
体A」と略す。)を含有することを特徴とする放射線感
応性重合体組成物
ならびに
に)側鎖にプロパルギル基および置換プロパルギル基を
有する重合体をハロゲン化することにより得られる重合
体(以下、「重合体B」と略す。)
を含有することを特徴とする放射線感応性重合体組成物
を提供するものである。[Means for Solving the Problems] The present invention comprises: (1) a polymer having a propargyl group and/or a substituted propargyl group and a sensitizing group in the side chain (hereinafter abbreviated as "polymer A"); A radiation-sensitive polymer composition characterized by: and (ii) a polymer obtained by halogenating a polymer having a propargyl group and a substituted propargyl group in the side chain (hereinafter abbreviated as "polymer B"). ) A radiation-sensitive polymer composition is provided.
本発明において重合体Aは水酸基、カルボキシル基など
の反応性基を有する(共)重合体(以下、「反応性重合
体」と略す。)の反応性基に、プロパルギル基および/
または置換プロパルギル基(以下、これらを「プロパル
ギル基等」と略す。)ならびに増感基を付与した(共)
重合体である。In the present invention, Polymer A is a (co)polymer having reactive groups such as hydroxyl groups and carboxyl groups (hereinafter abbreviated as "reactive polymer").
or a substituted propargyl group (hereinafter referred to as "propargyl group, etc.") and a sensitizing group (co-)
It is a polymer.
ここで反応性重合体としては、ポリアクリル酸、ポリメ
タクリル酸、ポリ(ヒドロキシスチレン)、ポリ (ヒ
ドロキシ−α−メチルスチレン)、ポリアミック酸、水
酸基を有するポリアミド、水酸基を有するポリエステル
、多糖類、カゼインなどを挙げることができ、好ましく
はポリアクリル酸、ポリメタクリル酸、ポリ(ヒドロキ
シスチレン)、ポリ(α−メチルヒドロキシスチレン)
などの側鎖にカルボキシル基や水酸基を有するアクリル
系ポリマーやスチレン系ポリマーを挙げることができる
。Here, the reactive polymers include polyacrylic acid, polymethacrylic acid, poly(hydroxystyrene), poly(hydroxy-α-methylstyrene), polyamic acid, polyamide having a hydroxyl group, polyester having a hydroxyl group, polysaccharide, casein. Preferably, polyacrylic acid, polymethacrylic acid, poly(hydroxystyrene), poly(α-methylhydroxystyrene), etc.
Examples include acrylic polymers and styrene polymers having carboxyl groups or hydroxyl groups in their side chains.
また、重合体Aが有するプロパルギル基等は、式
R’ C=−C−CR2R3−(式中、R1、R2
およびR3は同一または異なり、水素原子、メチル基、
エチル基、プロピル基、ブチル基などの炭素数1〜4の
アルキル基、フェニル基またはベンジル基を示す。)で
表わされる基であり、具体的には、プロパルギル基、3
−メチルプロパルギル基、1−メチルプロパルギル基、
1,1−ジメチルプロパルギル基、1.1−ジメチル−
3メチルプロパルギル基、3−エチルプロパルギル基、
1−エチルプロパルギル基、1,1−ジエチルプロパル
ギル基、3−フェニルプロパルギル基、1−フェニルプ
ロパルギル基、1,1−ジフェニルプロパルギル基、3
−ベンジルプロパルギル基、1−ベンジルプロパルギル
基、1−フェニル−3−メチルプロパルギル基などを挙
げることができる。In addition, the propargyl group, etc. that polymer A has has the formula
R' C=-C-CR2R3- (wherein, R1, R2
and R3 are the same or different, a hydrogen atom, a methyl group,
It represents an alkyl group having 1 to 4 carbon atoms such as an ethyl group, a propyl group, a butyl group, a phenyl group, or a benzyl group. ), specifically, propargyl group, 3
-methylpropargyl group, 1-methylpropargyl group,
1,1-dimethylpropargyl group, 1,1-dimethyl-
3-methylpropargyl group, 3-ethylpropargyl group,
1-ethylpropargyl group, 1,1-diethylpropargyl group, 3-phenylpropargyl group, 1-phenylpropargyl group, 1,1-diphenylpropargyl group, 3
Examples include -benzylpropargyl group, 1-benzylpropargyl group, and 1-phenyl-3-methylpropargyl group.
重合体Aにおいて、これらのプロパルギル基等は、前記
反応性重合体の有する全繰り返し単位の、通常、5〜9
9%、好ましくは40〜85%に付与されている。この
プロパルギル基の付与量が5%未満である場合、得られ
る重合体Aを放射線により架橋させた際に、架橋密度が
低くなる。In Polymer A, these propargyl groups usually account for 5 to 9 of the total repeating units of the reactive polymer.
9%, preferably 40-85%. If the amount of propargyl groups provided is less than 5%, the crosslink density will be low when the resulting polymer A is crosslinked by radiation.
さらに、重合体Aは増感基を有するものである。Furthermore, polymer A has a sensitizing group.
ここで増感基としては、ナフチル基、アントラニル基な
ど芳香族縮合環系の基、およびこれら芳香族縮合環系の
基を置換基として有するメチル基、エチル基、プロピル
基、ブチル基などの炭素数1〜4のアルキル基、ベンゾ
イルフェニル基、アントラキノニル基などの芳香族ケト
ン系の基、およびこれら芳香族ケトン系の基を置換基と
して有するメチル基、エチル基、プロピル基、ブチル基
などの炭素数1〜4のアルキル基などが挙げられる。Here, the sensitizing group includes aromatic condensed ring groups such as naphthyl groups and anthranyl groups, and carbon atoms such as methyl, ethyl, propyl, and butyl groups having these aromatic condensed ring groups as substituents. Aromatic ketone groups such as alkyl groups of numbers 1 to 4, benzoylphenyl groups, anthraquinonyl groups, and carbon atoms such as methyl groups, ethyl groups, propyl groups, butyl groups having these aromatic ketone groups as substituents Examples include alkyl groups of numbers 1 to 4.
重合体Aにおいて、この増感基は前記反応性重合体の有
する全繰り返しの単位の、通常、1〜30%、好ましく
は5〜15%に付与されている。In Polymer A, this sensitizing group is usually added to 1 to 30%, preferably 5 to 15% of the total repeating units of the reactive polymer.
反応性重合体にプロパルギル基等を導入する方法として
は、反応性重合体と炭素数1〜4のアルキル基を置換基
として有しうる臭化プロパルギル、塩化プロパルギル、
フッ化プロパルギル、ヨウ化プロパルギルなどのハロゲ
ン化プロパルギルとを・塩基性触媒の存在下20〜80
℃で反応させて、反応性重合体の反応性基の一部がプロ
パルギル化された重合体(以下、「重合体A−IJと略
す。)を得る方法が挙げられる。As a method for introducing a propargyl group etc. into a reactive polymer, a reactive polymer and propargyl bromide, propargyl chloride, which can have an alkyl group having 1 to 4 carbon atoms as a substituent,
with propargyl halides such as propargyl fluoride and propargyl iodide in the presence of a basic catalyst.
A method for obtaining a polymer (hereinafter abbreviated as "polymer A-IJ") in which some of the reactive groups of the reactive polymer are propargylated by reacting at .degree. C. can be mentioned.
この反応において、反応性重合体に対するハロゲン化プ
ロパルギルの使用量は反応性重合体の反応性基1グラム
当量に対して、好ましくは0.05〜2モル、特に好ま
しくは0.5〜2モルである。ハロゲン化プロパルギル
の使用量がOo 05モル未満では、生成する重合体A
−I中のプロパルギル基等の量が少なく、十分な放射線
感応性が得られない。In this reaction, the amount of propargyl halide used in the reactive polymer is preferably 0.05 to 2 mol, particularly preferably 0.5 to 2 mol, per gram equivalent of the reactive group of the reactive polymer. be. If the amount of propargyl halide used is less than 0.05 moles, the produced polymer A
-I has a small amount of propargyl groups, etc., and sufficient radiation sensitivity cannot be obtained.
また、塩基性触媒としては、ピリジン、トリエチルアミ
ン、1,8−ジアザビシクロ−[5,4゜0〕−ウンデ
セン−7(以下、rDBUJと略す。)などの含窒素有
機化合物が挙げられ、塩基性触媒の使用量は、ハロゲン
化プロパルギル1モルに対して、好ましくは1〜20モ
ル、特に好ましくは1〜5モルである。In addition, examples of the basic catalyst include nitrogen-containing organic compounds such as pyridine, triethylamine, and 1,8-diazabicyclo-[5,4°0]-undecene-7 (hereinafter abbreviated as rDBUJ). The amount used is preferably 1 to 20 mol, particularly preferably 1 to 5 mol, per 1 mol of propargyl halide.
重合体A−Iを得る反応では、塩基性触媒自体を反応溶
媒とすることができるが、反応系の粘度が高い場合には
希釈溶媒を用いることもできる。In the reaction to obtain the polymer A-I, the basic catalyst itself can be used as a reaction solvent, but if the viscosity of the reaction system is high, a diluting solvent can also be used.
ここで用いる希釈溶媒としては、例えばジメチルホルム
アミド、ジメチルスルホキシドなどの非プロトン性溶媒
、アセトン、メチルエチルケトン、シクロヘキサノンな
どのケトン系溶媒、およびジオキサン、テトラヒドロフ
ランなどの環状エーテルが挙げられる。Examples of the diluting solvent used here include aprotic solvents such as dimethylformamide and dimethyl sulfoxide, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and cyclic ethers such as dioxane and tetrahydrofuran.
反応終了後、酢酸などを用いて反応系を中和し、さらに
大過剰の水やイソプロパツール、アルコール類のような
貧溶媒によって重合体A−1を析出させ回収する。なお
回収した重合体A−1は、テトラヒドロフラン、ジオキ
サンなどの良溶媒に溶解し、不溶分を一過した後、貧溶
媒によって再沈殿することにより精製することができる
。After the reaction is completed, the reaction system is neutralized using acetic acid or the like, and the polymer A-1 is precipitated and recovered using a large excess of water, isopropanol, or a poor solvent such as alcohol. Note that the recovered polymer A-1 can be purified by dissolving it in a good solvent such as tetrahydrofuran or dioxane, passing away insoluble matter, and then reprecipitating it with a poor solvent.
このようにして得られた重合体A−Iに、さらに増感基
を導入する方法としては、重合体A−Iと1−クロロナ
フタレン、2−ブロモメチルアントラセン、2−ブロモ
メチルアントラキノンなどの、
一般式 W−Z
(式中、Wはフッ素原子、ヨウ素原子、塩素原子、臭素
原子などのハロゲン原子または炭素数1〜4のハロゲン
化アルキル基を、Zは前記と同様の増感基を示す)
で表わされる化合物を、重合体A−1の合成の場合と同
様の溶媒に溶解し、重合体A−1の合成の場合と同様の
塩基性触媒存在下に、通常40〜100°Cに加熱し反
応させる方法が挙げられ、重合体Aの回収および精製は
重合体A−Iの場合と同様にして行なうことができる。As a method for further introducing a sensitizing group into the polymer A-I obtained in this way, polymer A-I and 1-chloronaphthalene, 2-bromomethylanthracene, 2-bromomethylanthraquinone, etc. General formula W-Z (wherein, W represents a halogen atom such as a fluorine atom, an iodine atom, a chlorine atom, a bromine atom, or a halogenated alkyl group having 1 to 4 carbon atoms, and Z represents a sensitizing group as described above) ) is dissolved in the same solvent as in the synthesis of polymer A-1, and heated at usually 40 to 100°C in the presence of a basic catalyst as in the synthesis of polymer A-1. Examples include a method of heating and reacting, and recovery and purification of Polymer A can be performed in the same manner as in the case of Polymer A-I.
なお重合体Aは後記する重合体Bの製造と同様にしてハ
ロゲンと反応させ、重合体Aの主鎖または側鎖をハロゲ
ン化して用いることもできる。The polymer A can also be used by reacting it with a halogen in the same manner as in the production of the polymer B described later to halogenate the main chain or side chain of the polymer A.
本発明において重合体Bは、重合体A−1と塩素、臭素
、ヨウ素、フッ素などのハロゲンとをジクロルメタンな
どのハロゲン化溶媒中で、通常0℃以下、好ましくは−
5〜−10℃で反応させることによって合成することが
できる。In the present invention, Polymer B is prepared by combining Polymer A-1 and a halogen such as chlorine, bromine, iodine, or fluorine in a halogenated solvent such as dichloromethane at a temperature usually below 0°C, preferably -
It can be synthesized by reacting at 5 to -10°C.
重合体A−1に対して使用されるハロゲンの量は、重合
体A−1が有するプロパルギル基等1グラム当量当り、
好ましくは0.5〜3モル、特に好ましくは1〜2.5
モルである。このハロゲンの量が0.5モル未満では、
生成する重合体中Bのハロゲンの量が少なくなり、十分
な放射線感応性が得られない。The amount of halogen used for the polymer A-1 is per gram equivalent of propargyl group, etc., which the polymer A-1 has,
Preferably 0.5 to 3 mol, particularly preferably 1 to 2.5 mol
It is a mole. If the amount of halogen is less than 0.5 mol,
The amount of halogen B in the resulting polymer decreases, making it impossible to obtain sufficient radiation sensitivity.
反応終了後、n−ヘキサン、n−へブタンなどの炭化水
素溶媒によって重合体Bを析出させ回収する。また回収
した重合体Bは、テトラヒドロフランなどの良溶媒に溶
解し、貧溶媒で再沈殿することにより精製することがで
きる。After the reaction is completed, polymer B is precipitated and recovered using a hydrocarbon solvent such as n-hexane or n-hebutane. Moreover, the recovered polymer B can be purified by dissolving it in a good solvent such as tetrahydrofuran and reprecipitating it in a poor solvent.
重合体Bに含まれるハロゲンの量は、重合体Bの全繰り
返し単位1グラム当量に対して、通常0゜02〜4グラ
ム当量、好ましくは0.2〜2グラム当量である。The amount of halogen contained in Polymer B is generally 0.02 to 4 gram equivalents, preferably 0.2 to 2 gram equivalents, per 1 gram equivalent of all repeating units of Polymer B.
さらに、本発明において、重合体AまたはBは、該重合
体を合成する際に反応性重合体として、例えばポリアク
リル酸、ポリメタクリル酸などの側鎖にカルボキシル基
を有する重合体を用い、プロパルギル基等ならびに増感
基および/またはハロゲン原子の導入後にもカルボキシ
ル基の5%以上、好ましくは20%以上を残存させ、該
残存カルボキシル基を塩基性化合物を用いて中和するこ
とにより水溶性にすることもできる。Furthermore, in the present invention, when synthesizing the polymer A or B, a polymer having a carboxyl group in the side chain, such as polyacrylic acid or polymethacrylic acid, is used as a reactive polymer, and a propargyl 5% or more, preferably 20% or more of the carboxyl groups remain after the introduction of the groups, sensitizing groups and/or halogen atoms, and the remaining carboxyl groups are neutralized with a basic compound to make them water-soluble. You can also.
カルボキシル基の中和に用いる塩基性化合物としては、
水酸化カリウム、水酸化ナトリウムなどの無機アルカリ
、N (CH3)40H1HOCH2CH2N (CH
3)5・OHなどの4級アンモニウム塩、アンモニア、
トリメチルアミンなどのアミン類を用いることができる
。この中和反応は、通常、重合体A−1の合成において
用いられる溶剤と同様の溶剤に溶解した重合体Aまたは
Bに、メタノール、エタノールなどに溶解した塩基性化
合物を加えて室温で反応させることにより行なう。反応
終了後、反応液をエーテルなどによって水溶化した重合
体AまたはBを析出させ回収する。Basic compounds used to neutralize carboxyl groups include:
Inorganic alkalis such as potassium hydroxide and sodium hydroxide, N (CH3)40H1HOCH2CH2N (CH
3) Quaternary ammonium salts such as 5-OH, ammonia,
Amines such as trimethylamine can be used. This neutralization reaction is usually performed by adding a basic compound dissolved in methanol, ethanol, etc. to polymer A or B dissolved in the same solvent as used in the synthesis of polymer A-1, and reacting at room temperature. Do it by doing this. After the reaction is completed, the reaction solution is made water-soluble with ether or the like, and the polymer A or B is precipitated and recovered.
本発明の組成物は、前記重合体AまたはBを溶媒、例え
ばクロロベンゼン、キシレン、エチルベンゼン、トルエ
ン、アニソールなどの芳香族系溶媒、シクロヘキサノン
、メチルエチルケトンなどのケトン系溶媒、クロロホル
ム、四塩化炭素、トリクロロエタンなどの塩素系溶媒、
またはメチルセロソルブアセテート、ジグライムなどの
グリコール系溶媒に重合体AまたはBを溶解したもので
ある。ここで、重合体AまたはBの溶液中濃度は、一般
には5〜30重量%である。なお、重合体AまたはBが
水溶化されている場合には、水を溶媒とすることもでき
る。In the composition of the present invention, the polymer A or B can be used in a solvent such as an aromatic solvent such as chlorobenzene, xylene, ethylbenzene, toluene, anisole, a ketone solvent such as cyclohexanone or methyl ethyl ketone, chloroform, carbon tetrachloride, trichloroethane, etc. chlorinated solvents,
Alternatively, polymer A or B is dissolved in a glycol solvent such as methyl cellosolve acetate or diglyme. Here, the concentration of polymer A or B in solution is generally 5 to 30% by weight. In addition, when the polymer A or B is water-solubilized, water can also be used as a solvent.
本発明の組成物には、必要に応じて安定剤(老化防止剤
)などを添加することができる。A stabilizer (anti-aging agent) or the like can be added to the composition of the present invention, if necessary.
この安定剤としては、例えばヒドロキノン、メトキシフ
ェノール、p−t−ブチルカテコール、2.2′−メチ
レンビス(6−t−ブチル−4−エチルフェノール)な
どのフェノール系化合物、ベンゾキノン、p−トルキノ
ン、p−キシロキノンなどのキノン類、フェニル−α−
ナフチルアミン、P、P’ −ジフェニルフェニレンジ
アミンなどのアミン類、およびジラウリルチオジプロピ
オナート、4,4−チオビス(6−t−ブチル−3−メ
チルフェノール) 、2.2’−チオビス(4−メチル
−6−t−ブチルフェノール)、2−(3,5−ジ−t
−ブチル−4−ヒドロキシアニリノ’) −4,6−ビ
ス(N−オクチルチオ)−δ−トリアジンなどの硫黄化
合物が挙げられ、その添加量は本発明の重合体Aまたは
重合体Bに対して、通常0.5〜5重量%である。Examples of the stabilizer include phenolic compounds such as hydroquinone, methoxyphenol, p-t-butylcatechol, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), benzoquinone, p-tolquinone, p- -quinones such as xyloquinone, phenyl-α-
Amines such as naphthylamine, P,P'-diphenylphenylenediamine, and dilaurylthiodipropionate, 4,4-thiobis(6-t-butyl-3-methylphenol), 2,2'-thiobis(4- methyl-6-t-butylphenol), 2-(3,5-di-t
Sulfur compounds such as -butyl-4-hydroxyanilino') -4,6-bis(N-octylthio)-δ-triazine are mentioned, and the amount added is determined based on the polymer A or polymer B of the present invention. , usually 0.5 to 5% by weight.
本発明の組成物をレジストとして用いる場合には、前記
のようにして調製された組成物をシリコンウェーハなど
の基板上にスピンナーなどで塗布し、乾燥して皮膜を形
成させ、次いで、この皮膜上に放射線を所定のパターン
形状に照射することにより、放射線照射部分の重合体A
またはBを架橋し、未架橋部分を現像により除去するこ
とによりネガ型のレジストパターンを得る。When the composition of the present invention is used as a resist, the composition prepared as described above is applied onto a substrate such as a silicon wafer using a spinner, dried to form a film, and then coated on the film. By irradiating radiation in a predetermined pattern shape, the polymer A in the radiation irradiated area is
Alternatively, a negative resist pattern is obtained by crosslinking B and removing the uncrosslinked portion by development.
ここで、現像液としては、メチルエチルケトン、アセト
ン、シクロヘキサノンなどのケトン系溶剤、酢酸ブチル
、酢酸エチルなどのエステル系溶剤、セロソルブ、メチ
ルセロソルブなどのグリコールエステル系溶剤、ジオキ
サン、テトラヒドロフランなどの環状エーテル系溶剤、
あるいはこれらの溶剤と本発明の組成物の調製に用いる
溶媒、エタノール、イソプロパツールなどのアルコール
系溶剤またはn−ヘキサン、n−ヘプタンなどの脂肪族
系溶剤との混合溶媒を例示することができる。Here, the developer includes ketone solvents such as methyl ethyl ketone, acetone, and cyclohexanone, ester solvents such as butyl acetate and ethyl acetate, glycol ester solvents such as cellosolve and methyl cellosolve, and cyclic ether solvents such as dioxane and tetrahydrofuran. ,
Alternatively, mixed solvents of these solvents and the solvent used for preparing the composition of the present invention, alcoholic solvents such as ethanol and isopropanol, or aliphatic solvents such as n-hexane and n-heptane can be exemplified. .
さらに重合体AまたはBが水溶化されている場合には水
を現像液として用いることができる。レジストパターン
が形成された基板は、50〜200℃で乾燥および熱処
理され、エツチングその他の処理に供される。Furthermore, if the polymer A or B is water-solubilized, water can be used as the developer. The substrate on which the resist pattern has been formed is dried and heat treated at 50 to 200°C, and subjected to etching and other treatments.
実施例1
(1)ポリアクリル酸(30℃、DMF中0.5g/d
lにおける還元粘度0.34瀬/g)17゜3g(モノ
マーユニット単位0. 24mol )をジメチルスル
ホキシド200@1に溶解し、臭化プロパルギル17.
3g (0,14mol )とDBU40、 19g
(0,26mol )を加えて、50℃で1時間反応
させた。次いで酢酸100dを反応液に加えて中和し、
水中に注ぎ、沈殿したポリマーヲ回収し、テトラヒドロ
フランおよび水を用いて1回、テトラヒドロフランおよ
びエーテルを用いて1回再沈殿し、50℃で減圧乾燥し
たところ、ポリアクリル酸の有するカルボキシル基の6
0%にプロパルギル基が付加した重合体A−Iを10゜
3g得た。この重合体A−1をポリマー■とする。Example 1 (1) Polyacrylic acid (30°C, 0.5 g/d in DMF
Propargyl bromide 17.3 g (monomer unit 0.24 mol) was dissolved in dimethyl sulfoxide 200@1.
3g (0.14mol) and DBU40, 19g
(0.26 mol) was added and reacted at 50°C for 1 hour. Next, 100 d of acetic acid was added to the reaction solution to neutralize it,
The precipitated polymer was recovered by pouring into water, and reprecipitated once with tetrahydrofuran and water, once with tetrahydrofuran and ether, and dried under reduced pressure at 50°C.
10.3 g of a polymer A-I containing 0% propargyl groups was obtained. This polymer A-1 is referred to as polymer (2).
(2) (1)で合成したポリマー■ 1gをジメチ
ルホルムアミド5−に溶解し、DBUo、645g(4
,2mmol)を加えた。この溶液にジメチルホルムア
ミド5m1に溶解した2−ブロモメチルアントラキノン
(BMAQ)0.105g (0,35mmol)を加
え、さらにメタノール5−を加え、50℃で24時間反
応させた。反応終了後、酢酸5−を加えて反応液を中和
し、大量の水に注いで沈殿した重合体を回収した。さら
にテトラヒドロフランおよび水を用い1回、テトラヒド
ロフランおよびエーテルを用いて1回再沈殿精製し、5
0℃で減圧乾燥して、ポリアクリル酸の有するカルボキ
シル基の60%にプロパルギル基が、3.2%にメチル
アントラキノニル基が付加した重合体Aを得た。この重
合体をポリマー■とする。(2) Dissolve 1 g of the polymer ■ synthesized in (1) in dimethylformamide 5-, and add 645 g (4
, 2 mmol) was added. To this solution, 0.105 g (0.35 mmol) of 2-bromomethylanthraquinone (BMAQ) dissolved in 5 ml of dimethylformamide was added, and methanol 5- was further added, and the mixture was reacted at 50° C. for 24 hours. After the reaction was completed, the reaction solution was neutralized by adding 5-acetic acid and poured into a large amount of water to recover the precipitated polymer. Further, reprecipitation purification was performed once using tetrahydrofuran and water and once using tetrahydrofuran and ether, and 5
It was dried under reduced pressure at 0° C. to obtain a polymer A in which 60% of the carboxyl groups of polyacrylic acid had propargyl groups and 3.2% had methylanthraquinonyl groups. This polymer is referred to as Polymer (2).
(3) (2)で得られたポリマー■ 0.1gをメ
チルセロソルブに溶解して5重量%の溶液とし、スピン
コード法により銅板上に、乾燥膜厚で0.5μmとなる
よう塗布し、1時間風乾した。乾燥後、この上にコダッ
クステップタブレット阻2を重ね、3cmの距離から2
分間、250Wの超高圧水銀灯で光照射を行ない、次い
でメチルエチルケトン/酢酸エチル=15/85(重量
比)の混合液を現像液として5分間現像し、不溶化段数
を求めたところ12段であった。(3) Dissolve 0.1 g of the polymer ■ obtained in (2) in methyl cellosolve to make a 5% by weight solution, and apply it on a copper plate using a spin code method to a dry film thickness of 0.5 μm. It was air-dried for 1 hour. After drying, place Kodak Step Tablet 2 on top of this and hold it from a distance of 3 cm.
The film was irradiated with light using a 250 W ultra-high pressure mercury lamp for 5 minutes, and then developed using a 15/85 (weight ratio) mixture of methyl ethyl ketone/ethyl acetate as a developer for 5 minutes, and the number of insolubilization stages was determined to be 12.
ここで用いたステップタブレットは、照射する放射線の
強さが段階的に変化するよう透過度の異なる複数の部分
を配列して形成されており、透過度のレベルは数値(段
数)によって表わされ、不溶化段数は数値が大きくなる
ほど少ない放射線照射量で不溶化することを示すもので
ある。The step tablet used here is formed by arranging multiple parts with different transmittances so that the intensity of the irradiated radiation changes stepwise, and the level of transmittance is expressed by a numerical value (number of steps). , the number of insolubilization stages indicates that the larger the number, the smaller the amount of radiation irradiation required for insolubilization.
実施例2
(1)実施例1(2)で合成したポリマー■ 1gをテ
トラヒドロフラン50m1に溶解し、0.1規定の濃度
にした水酸化カリウムのメタノール溶液35.4−を加
えてカルボキシル基を中和した。この溶液を300−の
エーテル中に注ぎ、沈殿したポリマーを回収し、50℃
で減圧乾燥し、ポリマー2に残存するカルボキシル基の
全量をカルボン酸カリウム塩とした重合体A1.07g
得た。この重合体Aの還元粘度は、2. 02de/g
(30℃、0. 5g/de、水中)であった。この
重合体をポリマー■とする。Example 2 (1) 1 g of the polymer ■ synthesized in Example 1 (2) was dissolved in 50 ml of tetrahydrofuran, and 35.4 mm of a methanol solution of potassium hydroxide at a concentration of 0.1N was added to neutralize the carboxyl groups. It was peaceful. This solution was poured into 300°C ether, the precipitated polymer was collected, and the solution was heated to 50°C.
1.07 g of Polymer A was dried under reduced pressure to convert the entire amount of carboxyl groups remaining in Polymer 2 into carboxylic acid potassium salt.
Obtained. The reduced viscosity of this polymer A is 2. 02de/g
(30°C, 0.5 g/de, water). This polymer is referred to as Polymer (2).
(2) (1)で合成したポリマー■ 0.1gを水
に溶解して5重量%の溶液とし、スピンコード法により
銅板上に乾燥膜厚で10μmとなるよう塗布し、1時間
減圧乾燥した。次いで、この上にコダックステップタブ
レットNα2を重ね、250W超高圧水銀灯を用いて空
気中で3cmの距離から2分間光照射を行ない、水を現
像溶媒として5分間浸漬現像し、不溶化段数を求めたと
ころ16段であった。(2) 0.1 g of the polymer synthesized in (1) was dissolved in water to make a 5% by weight solution, which was applied onto a copper plate using a spin cord method to a dry film thickness of 10 μm, and dried under reduced pressure for 1 hour. . Next, Kodak Step Tablet Nα2 was placed on top of this, irradiated with light for 2 minutes from a distance of 3 cm in the air using a 250W ultra-high pressure mercury lamp, and immersed in water for 5 minutes to develop, and the number of insolubilization stages was determined. It was 16 steps.
比較例1
実施例1(1)で合成したポリマー■を5重量%となる
ようメチル七ロブに溶解し、これに増感剤として2−メ
チルアントラキノンを量を変えて添加、溶解し、それぞ
れにつき実施例1と同様にして光を照射し、アセトン/
メタノール=1/1 (容量比)の混合溶剤で現像し、
不溶化段数を求めた。Comparative Example 1 Polymer ■ synthesized in Example 1 (1) was dissolved in methyl hetamine to give a concentration of 5% by weight, and 2-methylanthraquinone was added and dissolved in varying amounts as a sensitizer. Light was irradiated in the same manner as in Example 1, and acetone/
Developed with a mixed solvent of methanol = 1/1 (volume ratio),
The number of insolubilization stages was determined.
2−メチルアントラキノンの添加量が、ポリマー1の全
繰り返し単位1グラム当量に対して0.06グラム当量
のときに最も感度が高かったが、このときの不溶化段数
は4段であり、ポリマー側鎖に増感基を導入した実施例
1の場合よりも増感効果は低かった。The highest sensitivity was obtained when the amount of 2-methylanthraquinone added was 0.06 gram equivalent per gram equivalent of all repeating units of Polymer 1, but the number of insolubilization stages at this time was 4, and the polymer side chain The sensitizing effect was lower than that of Example 1, in which a sensitizing group was introduced into the sample.
比較例2
比較例1において、増感剤を加えない以外は比較例1と
同様にして不溶化段数を求めたところ0段であった。Comparative Example 2 In Comparative Example 1, the number of insolubilization stages was determined in the same manner as in Comparative Example 1 except that no sensitizer was added, and it was found to be 0 stages.
実施例3
(1)実施例1(1)で合成したポリマー■ 0.60
6gをジクロルメタン4−に溶解し、0℃以下に冷却し
た後、臭素0. 5@f (9,8mmol)をジクロ
ルメタン2−に溶解した溶液を滴下し、3時間反応させ
た。反応終了後、反応液をn−ヘキサン50affに入
れ、沈殿したポリマーをデカンテーションして回収し、
テトラヒドロフラン−水系で1回、テトラヒドロフラン
−〇−ヘキサン系で1回再沈殿し、減圧乾燥して0.9
1gの精製重合体Bを得た。この重合体Bの還元粘度は
0.26dfl/g (0,5g/dfl、30℃、D
MF中)であり、重合体Bの有する全繰り返し単位1グ
ラム当量に対して1.9グラム当量の臭素を含有してい
た。得られた重合体Bをポリマー■とじた。Example 3 (1) Polymer synthesized in Example 1 (1) ■ 0.60
After dissolving 6 g in dichloromethane and cooling to below 0°C, 0.6 g of bromine was dissolved. A solution of 5@f (9.8 mmol) dissolved in dichloromethane 2- was added dropwise and reacted for 3 hours. After the reaction was completed, the reaction solution was poured into 50 aff of n-hexane, and the precipitated polymer was collected by decantation.
Reprecipitate once with tetrahydrofuran-water system and once with tetrahydrofuran-〇-hexane system, and dry under reduced pressure to obtain 0.9
1 g of purified polymer B was obtained. The reduced viscosity of this polymer B is 0.26 dfl/g (0.5 g/dfl, 30°C, D
MF), and contained 1.9 gram equivalents of bromine per 1 gram equivalent of all repeating units possessed by Polymer B. The obtained Polymer B was bound with Polymer ①.
(21(1)で得られたポリマー■をセロソルブアセテ
ートに溶解し、15重量%の濃度の溶液とし、スピンコ
ード法によりシリコンウェー71上に乾燥膜厚が0.5
μmとなるように塗布した。(Polymer ① obtained in 21(1) was dissolved in cellosolve acetate to make a solution with a concentration of 15% by weight, and a dry film thickness of 0.5
It was coated in a thickness of μm.
ホットプレート上90℃で2分間プレベークした後、ヘ
リウム雰囲気下X線としてパラジウムLα線を用い照射
量を変えて、087μm厚の全吸収体付きの窒化硼素膜
よりなるマスクパターンを介して、プロキシミティーギ
ャップを20μmとしてX線照射を行なった。照射後、
エチルセロソルブで1分間浸漬現像し、メチルエチルケ
トン/イソプロピルアルコールで1分間リンスし、乾燥
して残膜率および解像度を測定した。残膜率が50%と
なる照射量は60mJ/crBであり、解像度は0.8
μmであった。After pre-baking on a hot plate at 90°C for 2 minutes, proximity was measured using palladium Lα rays as X-rays in a helium atmosphere and varying the irradiation dose through a mask pattern made of a 087 μm thick boron nitride film with a total absorber. X-ray irradiation was performed with a gap of 20 μm. After irradiation,
The film was developed by immersion in ethyl cellosolve for 1 minute, rinsed with methyl ethyl ketone/isopropyl alcohol for 1 minute, dried, and the remaining film rate and resolution were measured. The irradiation dose at which the residual film rate is 50% is 60 mJ/crB, and the resolution is 0.8
It was μm.
比較例3
実施例1(1)で合成したポリマー■を15重量%とな
るようにメチルセロソルブに溶解し、スピンコード法に
よりシリコンウェーハ上に乾燥膜厚が0.5μmとなる
ように塗布して、実施例3と同様にしてX線照射および
現像を行ない、残膜率および解像性を調べた。X線を照
射量500mJ/cT1まで照射したが、現像によって
ポリマーが溶解してしまいパターンが得られなかった。Comparative Example 3 Polymer (1) synthesized in Example 1 (1) was dissolved in methyl cellosolve to a concentration of 15% by weight, and coated on a silicon wafer with a dry film thickness of 0.5 μm using a spin code method. X-ray irradiation and development were carried out in the same manner as in Example 3, and the remaining film rate and resolution were examined. Although X-rays were irradiated to a dose of 500 mJ/cT1, the polymer was dissolved during development and no pattern could be obtained.
[発明の効果]
本発明に用いられるプロパルギル基等と増感基を側鎖に
有する重合体は、分子内に増感基を有するため溶液中あ
るいは成膜時に増感剤が析出するようなことがなく均一
な膜を形成することができ、また増感剤が昇華すること
もなく効果的な増感作用を得ることができる。[Effect of the invention] The polymer having a propargyl group, etc. and a sensitizing group in the side chain used in the present invention has a sensitizing group in the molecule, so there is no possibility that the sensitizer will precipitate in the solution or during film formation. It is possible to form a uniform film without any oxidation, and an effective sensitizing effect can be obtained without sublimation of the sensitizer.
また、側鎖にプロパルギル基等を有する重合体をハロゲ
ン化して得られる重合体は、放射線の照射に対して効率
的に架橋反応を起こすことができる。Further, a polymer obtained by halogenating a polymer having a propargyl group or the like in a side chain can efficiently undergo a crosslinking reaction when irradiated with radiation.
本発明の放射線感応性重合体組成物は、微細なレジスト
パターンを高精度かつ高感度に形成することができるた
め、特に高い解像度が要求される半導体集積回路、液晶
基板、印刷版、テレビシャドウマスクなどの製造におい
て用いられるネガ型レジストとして好適に使用できる。The radiation-sensitive polymer composition of the present invention can form fine resist patterns with high precision and high sensitivity, so it can be used in semiconductor integrated circuits, liquid crystal substrates, printing plates, television shadow masks, etc., which require particularly high resolution. It can be suitably used as a negative resist used in the production of products such as.
Claims (2)
ルギル基ならびに増感基を有する重合体を含有すること
を特徴とする放射線感応性重合体組成物。(1) A radiation-sensitive polymer composition characterized by containing a polymer having a propargyl group and/or a substituted propargyl group and a sensitizing group in its side chain.
ルギル基を有する重合体をハロゲン化することにより得
られる重合体を含有することを特徴とする放射線感応性
重合体組成物。(2) A radiation-sensitive polymer composition characterized by containing a polymer obtained by halogenating a polymer having a propargyl group and/or a substituted propargyl group in its side chain.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21577288A JPH0263055A (en) | 1988-08-30 | 1988-08-30 | Polymer composition sensitive for radiation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21577288A JPH0263055A (en) | 1988-08-30 | 1988-08-30 | Polymer composition sensitive for radiation |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0263055A true JPH0263055A (en) | 1990-03-02 |
Family
ID=16677970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21577288A Pending JPH0263055A (en) | 1988-08-30 | 1988-08-30 | Polymer composition sensitive for radiation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0263055A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05321025A (en) * | 1992-01-09 | 1993-12-07 | Chuko Kasei Kogyo Kk | Production of yarn |
JPH08284016A (en) * | 1995-04-05 | 1996-10-29 | Ishikawa Pref Gov | Biodegradable fiber |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5060218A (en) * | 1973-09-27 | 1975-05-24 | ||
JPS59168018A (en) * | 1983-03-15 | 1984-09-21 | Mitsubishi Petrochem Co Ltd | Production of photocurable resin |
JPS62253152A (en) * | 1986-04-26 | 1987-11-04 | Japan Synthetic Rubber Co Ltd | Radiation sensitive polymer composition |
JPS6368835A (en) * | 1986-08-16 | 1988-03-28 | チバ−ガイギ− アクチエンゲゼル シヤフト | Image formation |
JPS63146929A (en) * | 1986-12-10 | 1988-06-18 | Asahi Chem Ind Co Ltd | Curable wholly aromatic polyamide |
JPS63198045A (en) * | 1987-02-13 | 1988-08-16 | Agency Of Ind Science & Technol | Photosensitive polymer |
-
1988
- 1988-08-30 JP JP21577288A patent/JPH0263055A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5060218A (en) * | 1973-09-27 | 1975-05-24 | ||
JPS59168018A (en) * | 1983-03-15 | 1984-09-21 | Mitsubishi Petrochem Co Ltd | Production of photocurable resin |
JPS62253152A (en) * | 1986-04-26 | 1987-11-04 | Japan Synthetic Rubber Co Ltd | Radiation sensitive polymer composition |
JPS6368835A (en) * | 1986-08-16 | 1988-03-28 | チバ−ガイギ− アクチエンゲゼル シヤフト | Image formation |
JPS63146929A (en) * | 1986-12-10 | 1988-06-18 | Asahi Chem Ind Co Ltd | Curable wholly aromatic polyamide |
JPS63198045A (en) * | 1987-02-13 | 1988-08-16 | Agency Of Ind Science & Technol | Photosensitive polymer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05321025A (en) * | 1992-01-09 | 1993-12-07 | Chuko Kasei Kogyo Kk | Production of yarn |
JPH08284016A (en) * | 1995-04-05 | 1996-10-29 | Ishikawa Pref Gov | Biodegradable fiber |
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